JP4080056B2 - Hydraulic system using improved non-abrasive hydraulic fluid - Google Patents

Hydraulic system using improved non-abrasive hydraulic fluid Download PDF

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JP4080056B2
JP4080056B2 JP09722298A JP9722298A JP4080056B2 JP 4080056 B2 JP4080056 B2 JP 4080056B2 JP 09722298 A JP09722298 A JP 09722298A JP 9722298 A JP9722298 A JP 9722298A JP 4080056 B2 JP4080056 B2 JP 4080056B2
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wear
aliphatic
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abrasive
hydraulic fluid
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JPH10298574A (en
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エイチ.ブラウン スチュアート
ブルックハート トッド
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シェブロン・オロナイト・カンパニー・エルエルシー
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Rotary Pumps (AREA)
  • Details Of Reciprocating Pumps (AREA)
  • Reciprocating Pumps (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、ピストンポンプに改良された摩耗保護を与える油圧流体に関する。
【0002】
【従来の技術】
運動する装置及び静止した装置の両方で油圧流体装置が用いられている。これらの装置は、油圧シリンダー、バルブ、ポンプ、配管、フィルター、及び貯槽を有する。ポンプはアクチュエーター、モーター及び(又は)油圧シリンダーへ油圧流体を加圧して送り、機械部品の運動及び位置制御を与える。多くの装置では、油圧流体は摩耗に対する保護を与える潤滑剤としての機能も果たす。
【0003】
高圧装置中のポンプは、一般に二つの型、回転羽根ポンプ及び(又は)軸ピストンポンプである。高圧羽根ポンプは、非摩耗性及び酸化安定性を有する油圧流体を必要とする。これらの性質は一般に油圧流体中にジチオ燐酸亜鉛を使用することにより達成されている。ピストン型ポンプは、防錆及び酸化防止のための添加剤を必要とするが、ジチオ燐酸亜鉛を使用する必要はない。反対に、ジチオ燐酸亜鉛を含有する流体は、或る種のピストンポンプでは滑動する鋼・銅合金界面に有害であることが判明している。或る場合には、これはそのようなポンプの早い壊滅的な損傷をもたらしている。
【0004】
このための一つの解決方法は、高油圧ピストンポンプ及び羽根ポンプのための別の潤滑組成物の開発することであった。これらの別々の組成物は両方の型のポンプに対して満足できるものではない。羽根ポンプは、ジチオ燐酸亜鉛のような摩耗防止剤を含む潤滑剤を必要とするが、それはピストンポンプの銅合金部品を腐食する。防錆及び酸化防止油はピストンポンプで用いるのに充分であるが、羽根ポンプの鋼部品の摩耗を防ぐのに充分な表面反応性を有する添加剤を含んでいない。
【0005】
第二の解決方法は、両方の型のポンプで僅かな性能を与える流体を開発することであった。特に二つの型のポンプが同じ溜めからそれらの潤滑剤を引き出すようになっている用途では、一層強力な単一の油圧ポンプ潤滑剤に対する必要性が以前から感じられていた。
【0006】
この第二の解決方法の一例は、「ピストン及び羽根ポンプを有する油圧流体装置」(Hydraulic Fluid System With Piston And Vane Pumps)と題する米国特許第4,622,157号明細書でピーラー(Peeler)により記載されている。ピーラーは、潤滑粘度の油、ジチオ燐酸亜鉛及び硫化エステル・オレフィンを含む油圧流体を、両方の型のポンプが同じ溜めからそれらの潤滑剤を引き出すようになっている用途に用いることを記述している。この油圧流体は両方の型のポンプに対して有用であるが、ジチオ燐酸亜鉛と硫化エステル・オレフィンの組合せは油圧流体の熱安定性を悪くすることがある。
【0007】
東燃株式会社による特開平5−331477号公報(1993)には、(a)0.1〜7重量%の、ジチオ燐酸亜鉛、亜燐酸エステル、及び燐酸エステルの一種類又は混合物、及び(b)0.02〜3重量%のグリセリン脂肪族エステルを含む、パワーステアリング流体に特に関する油圧油組成物が記載されている。グリセリンエステルの目的は摩擦を減少させることにある。その公報は、回転羽根ポンプ及び軸ピストンポンプの両方を有する油圧装置にその油圧油組成物を用いることは教示も示唆もしていない。
【0008】
「安定化油圧流体組成物」(Stabilized Hydraulic Fluid Composition)と題する米国特許第4,210,541号明細書には、(a)基礎油、(b)0.1〜2.0体積%のC4 〜C12ビス(ジアルキルジチオ燐酸)亜鉛、(c)0.01〜1.0体積%の金属ジアルキルナフタレンスルホン酸塩、及び(d)0.01〜1.0重量%の脂肪酸イミダゾリンを含む非摩耗性油圧油が記載されている。この特許は、回転羽根ポンプ及び軸ピストンポンプの両方を有する油圧装置でその油圧油組成物を使用することは教示も示唆もしていない。
【0009】
「多成分安定化油圧流体」(Multicomponent Stabilized Hydraulic Fluid)と題する米国特許第4,210,542号明細書には、(a)基礎油、(b)0.1〜2.0体積%のC4 〜C12ビス(ジアルキルジチオ燐酸)亜鉛、(c)0.01〜1.0体積%の金属ホスホン酸塩、及び(d)0.01〜1.0重量%の脂肪酸イミダゾリンを含む非摩耗性油圧油が記載されている。この特許は、回転羽根ポンプ及び軸ピストンポンプの両方を有する油圧装置でその油圧油組成物を使用することは教示も示唆もしていない。
【0010】
「潤滑油組成物」(Lubricating Oil Compositions)と題する米国特許第4,530,771号明細書には、クランクケースエンジン中の燃料を節約するための硼酸化グリセリンエステルを含む潤滑油組成物が記載されている。それは油圧油組成物は教示していない。
【0011】
【発明が解決しようとする課題】
本発明は、羽根ポンプ及びピストンポンプの両方で満足に用いることができる非摩耗性油圧流体を与える。その非摩耗性油圧流体は、銅又は銅合金を含む摩耗表面を有するピストン型ポンプ、場合により鋼を含む摩耗表面を有する羽根型ポンプを有する油圧装置で用いられる。一つの態様として、その油圧装置はピストン型ポンプ及び羽根型ポンプの両方を有し、油圧流体は共通の溜めから引き出される。本発明は、ピストン型ポンプ及び羽根型ポンプの両方に潤滑を与える方法も提供し、特にピストン型ポンプと羽根型ポンプの組合せを有する油圧装置で用いるのに特に魅力的である。
【0012】
【課題を解決するための手段】
非摩耗性油圧流体は両方の型のポンプに有用である。それは主成分量(major amount)の潤滑粘度の油、少量(minor amount)の少なくとも一種類の金属ジチオ燐酸塩、及び少量の摩耗軽減剤を含む。別の態様として、非摩耗性油圧流体は、主成分量の潤滑粘度の油、少量の少なくとも一種類の金属ジチオ燐酸塩、及び摩耗軽減剤を混合することにより製造することができる。成分は相互作用することがあるので、油圧流体は未反応成分と共に、種々の成分の一種類以上の錯体又は反応生成物を含んでいてもよい。
【0013】
通常、油圧流体中に金属ジチオ燐酸塩を用いると、ピストンポンプの銅合金部品の接着剤及び(又は)腐食性摩耗を惹き起こすであろうが、特別な摩耗軽減剤を存在させると、通常伴われる摩耗問題を起こすことなく、金属ジチオ燐酸塩を使用することができるようになることを我々は見出している。
【0014】
金属ジチオ燐酸塩は、9個より少ない炭素原子を有するアルキル基を有するジアルキルジチオ燐酸亜鉛であるのが好ましい。非摩耗性油圧流体は、好ましくは2〜10mM/kg、一層好ましくは4〜6mM/kgの金属ジチオ燐酸塩を含む。好ましくはジアルキルジチオ燐酸亜鉛は、β−炭素の所で分岐した第一級アルコールから誘導されたものであり、例えば、ジ−2−エチルヘキシルジチオ燐酸亜鉛である。
【0015】
摩耗性軽減剤は、
(1) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(2) 脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(3) (1)及び(2)の混合物、
からなる群から選択される。
【0016】
摩耗軽減剤の各々の場合において、脂肪族基は実質的に直鎖であり、摩耗軽減剤は、少なくとも10個の炭素原子を有する。脂肪族基は飽和していても、していなくてもよく、それらは置換されていても、されていなくてもよい。
【0017】
非摩耗性油圧流体は、好ましくは0.01〜0.5重量%、一層好ましくは0.025〜0.25重量%、最も好ましくは0.05〜0.1重量%の摩耗軽減剤を含有する。
【0018】
摩耗軽減剤の脂肪族基は、実質的に硫黄を含まないが、それ程好ましくない態様としては、脂肪族基は、硫化された不飽和を含んでいてもよい。
【0019】
摩耗軽減剤は好ましくは10〜40個の炭素原子を有する。一層好ましくはそれは14〜24個の炭素原子を含む。
【0020】
一つの態様として、摩耗軽減剤は、脂肪族ポリオールエステル、脂肪族ポリオールエステルの硼酸誘導体、又は脂肪族ポリオールエステルと脂肪族ポリオールエステルの硼酸誘導体との混合物である。好ましくは摩耗軽減剤は、ポリオールのモノエステルであり、例えば、グリセリンモノオレエート、又はペンタエリスリトールモノオレエートである。摩耗軽減剤は、硼酸化グリセリンモノオレエート、又は硼酸化ペンタエリスリトールモノオレエートでもよい。
【0021】
別の態様として、摩耗軽減剤は、脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、又はそれらの混合物である。好ましくは摩耗軽減剤は脂肪酸アミン、例えば、オレイルアミン、脂肪酸ジアミン、例えば、N−オレイル−1,3−プロパンジアミン、又は2−(脂肪族)−4,5−ジヒドロ−1H−イミダゾール−1−アルカノール、例えば、2−(ヘプタデシル)−4,5−ジヒドロ−1H−イミダゾール−1−エタノールである。
【0022】
更に別の態様として、摩耗軽減剤は、(1)脂肪族ポリオールエステル、その硼酸誘導体、又はその混合物、及び(2)脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、又はそれらの混合物、の混合物である。
【0023】
一つの別の態様として、油圧流体は、ピストン型ポンプ及び羽根型ポンプの両方を有する油圧装置で用いられ、この場合そのピストン型ポンプは銅又は銅合金を含む摩耗表面を有し、羽根型ポンプは鋼含有摩耗表面を有する。この態様では、油圧流体は共通の溜めから引き出される。
【0024】
本発明の目的は、両方の型のポンプを有する油圧装置で有用な単一の油圧ポンプ潤滑剤を与えることである。それは、ポンプがそれらの潤滑剤を共通の溜めから引き出すようになっている場合に特に有用である。
【0025】
【発明の実施の形態】
広い態様として、本発明は、銅又は銅合金を含む摩耗表面を有するピストン型ポンプ、場合により鋼を含む摩耗表面を有する羽根型ポンプを有し、独特の非摩耗性油圧流体を用いた油圧装置を包含する。一つの態様として、その油圧装置は、ピストン型ポンプ及び羽根型ポンプの両方を有し、油圧流体はそれら両方の型のポンプのための共通の溜めから引き出される。
【0026】
ポンプ
ピストン型及び羽根型ポンプは当分野でよく知られており、多くの異なった供給業者から入手することができる。羽根型ポンプは、油圧流体が、一般に鋼から作られている羽根及びカム・リングを保護するためにジチオ燐酸亜鉛のような摩耗防止剤を含むことを必要とする。しかし、或るピストンポンプ、例えば、デニソン・ハイドローリックス(Denison Hydraulics)により製造されたものは、そのような摩耗防止剤を含む流体により拮抗された鋼滑動接触部の上に銅合金を用いている。油圧装置の使用者は、両方の型のポンプで用いることができる単一の流体を望んでいる。
【0027】
本発明で用いる油圧流体は、これら既知のピストン型及び羽根型ポンプのいずれでも用いることができる。特に、それは、銅又は銅合金を含む摩耗表面を有するピストン型ポンプ及び鋼を含む摩耗表面を有する羽根型ポンプで用いることができる。これらのピストン型及び羽根型ポンプは、米国特許第4,622,157号明細書(これは全ての目的に対し参考のため全体的にここに入れてある)中にピーラーにより記載されている。
【0028】
非摩耗性油圧流体
本発明で用いる非摩耗性油圧流体は、主成分量の潤滑粘度の油、少量の金属ジチオ燐酸塩、及び少量の摩耗軽減剤で、脂肪族ポリオールエステル、脂肪族ポリオールエステルの硼酸誘導体、脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、又はそれらの混合物である摩耗軽減剤を含む。
【0029】
潤滑粘度の油
本発明で用いる非摩耗性油圧流体は、主成分量の潤滑粘度の油を含有する。その油はどのような炭化水素系潤滑油又は合成基礎油ストックでもよい。それは合成又は天然原料から誘導されたものでもよく、パラフィン系、ナフテン系、アスファルト系、又はそれらの混合物でもよい。
【0030】
潤滑粘度の油は、蒸留、脱アスファルト化及び脱蝋のような物理的分離方法によって粗鉱物油から製造することができる。或はそれは、鉱物油留分の接触又は非接触水素化処理のような化学的転化により、又は物理的分離方法と化学的転化との組合せにより製造することもできる。或はそれは合成炭化水素基礎油でもよい。潤滑粘度の油は、40℃で5〜220cStの動粘性率(Kinematic Viscosity )を有するのが好ましい。
【0031】
金属ジチオ燐酸塩
本発明で用いる非摩耗性油圧流体は、少量の金属ジチオ燐酸塩を含んでいる。好ましくは金属ジチオ燐酸塩は市販されている第II族金属ジチオ燐酸塩であり、第II族金属が好ましくは亜鉛、マグネシウム、カルシウム、又はバリウムである。最も好ましくは、金属は亜鉛である。
【0032】
金属ジチオ燐酸塩はよく知られた極圧(EP)添加剤であり、有機置換金属ジチオ燐酸塩、好ましくは金属ジヒドロカルビルジチオ燐酸塩であり、この場合ヒドロカルビル基は3〜20個の炭素原子、好ましくは4〜12個の炭素原子を有する。当分野でよく知られているように、種々の金属化合物の混合物も用いることができる。有機置換金属ジチオ燐酸塩は、カルボキシ、ヒドロキシ、カルブアルコキシ等のような官能基を有する脂肪族基を有する。ヒドロカルビル基は脂肪族、脂環式、又は芳香族、又はそれらの混合物でもよい。
【0033】
最も好ましくは、金属ジチオ燐酸塩はジアルキルジチオ燐酸亜鉛であり、この場合アルキル基は3〜20個の炭素原子、好ましくは4〜12個の炭素原子、最も好ましくは9より少ない炭素原子を有する。好ましい亜鉛化合物は、β−炭素の所で分岐した第一級アルコールから誘導されたジアルキルジチオ燐酸亜鉛であり、例えば、ジ−2−エチルヘキシルジチオ燐酸亜鉛である。
【0034】
金属ジチオ燐酸塩化合物は、一般に油1kg当たり2〜10mM、好ましくは3〜8mM、一層好ましくは4〜6mMの濃度で存在し、この場合各金属ジチオ燐酸塩分子中に二つの燐原子及び一つの金属原子が存在するものと仮定する。この計算方法では、金属ジチオ燐酸塩濃度は燐含有量を測定することにより決定される。この金属ジチオ燐酸塩濃度を表す方法は、市販金属ジチオ燐酸塩が一般に中性及び塩基性物質の混合物であると言う認識に基づいており、従って、用いた市販材料の中には金属1原子当たり2原子より少ない燐が存在していてもよい。
【0035】
摩耗軽減剤
本発明で用いる非摩耗性油圧流体は、少量の摩耗軽減剤も含有する。摩耗軽減剤は、
(1) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(2) 脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(3) (1)と(2)の混合物、
からなる群から選択される。例えば、摩耗軽減剤は脂肪族ポリオールエステルと脂肪族イミダゾリンとの混合物にすることができる。
【0036】
摩耗軽減剤の脂肪族基は実質的に直鎖であり、摩耗軽減剤は少なくとも10個の炭素原子を含有する。脂肪族基は飽和していても不飽和でもよく、僅かな程度の分岐を持っていてもよい。脂肪族基は置換されていなくてもよく、或はそれらはカルボキシ、ヒドロキシ、カルブアルコキシ等のような官能基で置換されていてもよい。好ましくは脂肪族基は実質的に硫黄を含まないが、それ程好ましくない態様として脂肪族基は硫化された不飽和を含んでいてもよい。
【0037】
非摩耗性油圧流体は、好ましくは摩耗軽減剤を0.01〜0.5重量%含む。一層好ましくはそれは摩耗軽減剤を0.025〜0.25重量%含む。最も好ましくはそれは摩耗軽減剤を0.05〜0.1重量%含む。
【0038】
一つの態様として、摩耗軽減剤は脂肪族ポリオールエステル、脂肪族ポリオールエステルの硼酸誘導体、又は脂肪族ポリオールエステル及び(又は)それらの硼酸誘導体の混合物にすることができる。好ましくはその摩耗軽減剤は10〜40個の炭素原子を、一層好ましくは14〜24個の炭素原子を有する。
【0039】
脂肪族ポリオールエステルは、6〜30個の炭素原子、好ましくは8〜24個の炭素原子を有する飽和又は不飽和モノカルボン酸で多価アルコールをエステル化することにより製造することができるが、但し少なくとも一つのヒドロキシル基はエステル化されていないままになっているものとする。
【0040】
多価アルコールには、ジ−、トリ−、及びテトラ−エチレングリコールを含めたエチレングリコール;ジ−、トリ−、及びテトラ−プロピレングリコールを含めたプロピレングリコール;グリセリン;トリメチロールプロパン;ブタンジオール;ヘキサンジオール;ソルビトール;アラビトール;マンニトール;サクロース;フラクトース;グルコース;シクロヘキサンジオール;エリスリトール;及びジ−及びトリ−ペンタエリトリトールを含めたペンタエリトリトールが含まれる。好ましくはトリオールはグリセリン、ペンタエリスリトール、トリメチロールプロパン、又はソルビトールである。
【0041】
モノカルボン酸の例には、脂肪カルボン酸が含まれる。脂肪酸エステルは当分野でよく知られた種々の方法により製造することができる。これらエステルの多くは商業的規模で製造されている。本発明で用いられるエステルは油に可溶性であり、天然生成物中に見出されているように、C6 〜C30脂肪酸又はその混合物から製造するのが好ましい。脂肪酸は飽和していてもしていなくてもよい。天然原料からの酸中に見出される或る化合物にはリカン酸が含まれ、それは一つのケト基を含む。好ましい脂肪酸は式R1 −COOH(式中、R1 はアルキル又はアルケニルである)の脂肪酸である。好ましい脂肪酸の例は、オレイン、ステアリン、パルミチン、ミリスチン、パルミトール、リノレイン、ラウリン、及びエレオステアリン、及び天然生成物、タロー、パーム油、オリーブ油、ピーナッツ油、コーン油、牛脚油等からの酸である。屡々酸は一種類以上の酸の混合物として市販されている。
【0042】
適当なエステル化多価アルコールの特別な例には、モノ−及びジ−オレエートを含めたオレイン酸ソルビトール;モノ−及びジ−ステアレートを含めたステアリン酸ソルビトール;グリセリンモノ−及びジ−オレエートを含めたグリセリンオレエート;及びオクタン酸エリスリトールが含まれる。好ましい例は、グリセリンモノオレエート及びペンタエリスリトールモノオレエート、及びそれらの硼酸化誘導体である。
【0043】
脂肪族ポリオールエステルはモノエステルであるのが好ましいが、ジ−及びトリ−エステルを混合物の一部分にすることができる。モノ−及びジ−エステルの混合物は、少なくとも40重量%のモノエステルを含むのが好ましい。最も好ましくは、モノ−及びジ−エステルの混合物は40〜60重量%のモノエステルを含む。例えば、市販グリセリンモノオレエートは、45〜55重量%のモノエステルと55〜45重量%のジエステルとの混合物を含んでいる。
【0044】
適当な硼酸エステルは上で引用した米国特許第4,530,771号明細書(これは全ての目的のために参考のため全体的にここに入れてある)に記載されている。
【0045】
本発明で有用な硼酸エステルは、反応物の種類、導入比、及び反応条件により構造が変化している種々の化合物を包含していてもよい。それらは単独で用いてもよく、又は組合せて用いてもよい。
【0046】
ポリオールがグリセリンである場合、典型的な硼酸エステルは次の式(I)及び(II)によって表される化合物又はそれらの混合物である。
【0047】
【化1】

Figure 0004080056
【0048】
【化2】
Figure 0004080056
【0049】
式中、X、Y、及びZは、独立にOH基又は
【0050】
【化3】
Figure 0004080056
【0051】
基を表し、ここでR′は7〜23個の炭素原子を有する飽和又は不飽和脂肪族基を表す。
【0052】
本発明で用いられる硼酸エステルは、例えば、次の方法、
(a) ポリオールエステルと硼酸とを100℃〜230℃の温度で反応させる、
(b) ポリオールと硼酸とを反応させ、更に得られた化合物をカルボン酸、カルボン酸の低級アルコールエステル、又はカルボン酸ハロゲン化物と反応させる、
(c) ポリオール、ポリオールのカルボン酸トリエステル、及び硼酸の混合物を約240℃〜280℃の温度で反応させる、
方法により製造することができる。
【0053】
別の態様として、摩耗軽減剤は窒素化合物でもよく、例えば、脂肪族アミン、脂肪族ポリアミン、脂肪族イミダゾリン、又はそれらの混合物でもよい。摩耗軽減剤は、好ましくは10〜40個の炭素原子、一層好ましくは14〜24個の炭素原子を有する。
【0054】
脂肪族アミンは一般式R″NH2 (式中、R″基は脂肪酸から誘導することができる)を有することができる。好ましいR″基は、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、パルミトール酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸等を含めた一層一般的な天然産脂肪酸から誘導されたものである。一層好ましくは脂肪族アミンはオレイルアミンである。
【0055】
本発明で用いられる脂肪族ポリアミンは、好ましくは少なくとも一つの末端アミノ窒素原子を有する。脂肪族ポリアミンは10〜40、好ましくは14〜24の全炭素原子、及び少なくとも二つの窒素原子を分子中に有する。夫々の場合で、アミノ窒素は少なくとも二つの炭素原子によって互いに分離されている。脂肪族ポリアミンのポリアミン部分は、約1:1〜2:1の炭素対窒素比を有するのが好ましい。ポリアミン部分の塩基性窒素原子の少なくとも一つは第一級又は第二級アミノ窒素であるべきである。本発明の脂肪族ポリアミンに適したポリアミン部分は、ルイス(Lewis)及びホネン(Honnen)による米国特許第4,191,537号及びチャーペック(Cherpeck)による米国特許第5,413,614号明細書(これらは全ての目的のため参考のため全体的にここに入れてある)に記載されている。好ましくは、脂肪族ポリアミンは、脂肪族エチレンジアミン、脂肪族プロパンジアミン、又は脂肪族ジエチレントリアミンである。特に好ましい具体例は、N−オレイン−1,3−プロパンジアミンである。
【0056】
好ましい種類の窒素化合物は、上で引用した米国特許第4,210,541号及び第4,210,542号明細書に記載されているように、脂肪族イミダゾリンである。これらの特許の両方共、全ての目的のため参考のため全体的にここに入れてある。
【0057】
脂肪族イミダゾリンは、一般式:
【0058】
【化4】
Figure 0004080056
【0059】
(式中、nは0〜3の整数、好ましくは1であり、Rは7〜35個の炭素原子、好ましくは9〜23個の炭素原子を有する脂肪族である。)
を有する2−(脂肪族)−4,5−ジヒドロ−1H−イミダゾール−1−アルカノールであるのが好ましい。R基はその化合物を製造するための方法で脂肪酸から誘導することができるので、好ましいR基は、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、パルミトール酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸等を含めた一層一般的な天然産脂肪酸から誘導されたものである。好ましくは脂肪族イミダゾリンは2−(ヘプタデシル)−4,5−ジヒドロ−1H−イミダゾール−1−エタノールである。
【0060】
しかし、一般的に脂肪族イミダゾリンは化合物の混合物になる。なぜなら、天然産脂肪酸は殆ど一般に混合物として入手されているからである。例えば、ステアリン酸、パルミチン酸、及びオレイン酸の混合物はタローから得られる。従って、タロー脂肪酸から製造された脂肪族イミダゾリンは、Rがヘキサデシル、オクタデシル、及び9−オクタデシルである化合物の混合物である。
【0061】
摩耗軽減剤の極性基は、それがエステル基又は窒素含有基であっても、脂肪族基の末端にあるのが好ましい。
【0062】
他の添加剤
当分野でよく知られている他の添加剤が、本発明で用いる非摩耗性油圧流体中に存在していてもよい。例えば、これらの添加剤には、酸化防止剤、粘度指数改良剤、分散剤、清浄剤、防錆剤、解乳化剤、発泡防止剤、腐食防止剤、流動点降下剤、及び他の摩耗防止剤が含まれる。これらの添加剤の例を下に示す。
【0063】
酸化防止剤:立体障害を持つアルキルフェノール、例えば、2,6−ジ−t−ブチルフェノール、2,6−ジ−t−ブチル−p−クレゾール、及び2,6−ジ−t−ブチル−4−(2−オクチル−3−プロパノイック)フェノール;N, N−ジ(アルキルフェニル)アミン;及びアルキル化フェニレンジアミンが含まれる。
【0064】
粘度指数改良剤;重合体アルキルメタクリレート及びオレフィン共重合体、例えば、エチレンプロピレン共重合体、又はスチレンブタジエン共重合体が含まれる。
【0065】
分散剤:ヒドロカルビルスクシンイミド、コハク酸エステル、又はベンジルアミンが含まれ、この場合ヒドロカルビル基は約700〜3000の分子量を有するアルキル又はアルケニル基である。これらの化合物は更に硼酸と反応させてもよい。
【0066】
清浄剤:アルキルサリチル酸カルシウム及びカルシウムアルキルフェネートが含まれる。
【0067】
防錆剤:アルケニルコハク酸、それらの部分エステル、及びそれらの窒素誘導体;及び金属ジノニルナフタレンスルホネートのような合成アルキルアリールスルホネートが含まれる。
【0068】
解乳化剤:アルコキシル化フェノール及びフェノールホルムアルデヒド樹脂及び合成アルキルアリールスルホネート、例えば、金属ジノニルナフタレンスルホネートが含まれる。
【0069】
発泡防止剤:アルキルメタクリレート重合体及びジメチルシリコーン重合体が含まれる。
【0070】
腐食防止剤:2,5−ジメルカプト−1,3,4−チアジアゾール及び誘導体、メルカプトベンゾチアゾール、アルキルトリアゾール、及びベンゾトリアゾールが含まれる。
【0071】
流動点降下剤:ポリメタクリレートが含まれる。
【0072】
他の摩耗防止剤:アリールホスフェート及びホスファイト、硫化エステル、及び硫黄・燐化合物が含まれる。
【0073】
一つの態様として、本発明で用いられる非摩耗性油圧流体は、潤滑粘度の油、金属ジチオ燐酸塩、摩耗軽減剤、及び他の添加剤を混合することにより製造することができる。別の態様として、非摩耗性油圧流体は、金属ジチオ燐酸塩、摩耗軽減剤、及び他の添加剤と、少量の希釈剤油、例えば、ケロセン、ディーゼル燃料、又は芳香族溶媒を混合し、濃厚な添加剤溶液を与えることにより製造することができ、その濃厚な添加剤溶液を潤滑粘度の油と混合してもよい。成分は相互作用を起こすことがあるので、油圧流体は、未反応成分と共に、種々の成分の一種類以上の錯体又は反応生成物を含んでいてもよい。
【0074】
【実施例】
本発明を、特に有利な方法の態様を記載した次の実施例により更に例示する。実施例は本発明を例示するために与えられているが、それらは本発明を限定するものではない。
【0075】
比較例A:ジ−2−エチルヘキシルジチオ燐酸亜鉛、及び機能的に有効な量のカルシウム清浄剤、防錆剤、解乳化剤、酸化防止剤、及び発泡防止添加剤の混合物を含む基礎添加剤配合物をパラフィン基礎油中に混合し、基礎添加剤配合物が最終油混合物の0.80重量%を構成するようにした。最終油混合物は、40℃で約46cStの動粘性率を持っていた。
【0076】
例1:比較例Aの最終油に、0.05重量%の市販グリセリンモノオレエートを添加した。
【0077】
比較例B:溶媒精製パラフィン基礎油中に、4mM/kgの市販ジチオ燐酸亜鉛及び2mM/kgの過塩基性カルシウムフェネートを混合した。最終油混合物は40℃で約46cStの動粘性率を持っていた。
【0078】
例2:比較例Bの最終油に、0.10重量%の市販グリセリンモノオレエートを混合した。
【0079】
比較例C:ジ−2−エチルヘキシルジチオ燐酸亜鉛、及び機能的に有効な量のカルシウム清浄剤、防錆剤、解乳化剤、酸化防止剤、及び発泡防止添加剤の混合物を含む市販非摩耗性油圧油基礎添加剤配合物を、溶媒精製したパラフィン基礎油中に混合し、基礎添加剤配合物が最終油混合物の1.13重量%を構成するようにした。最終油混合物は、40℃で約46cStの動粘性率を持っていた。
【0080】
例3:比較例Cの最終油に、0.10重量%の硼酸化グリセリンモノオレエートを添加した。
【0081】
例4:比較例Cの最終油に、0.10重量%の市販N−オレイル−1,3−プロパンジアミンを添加した。
【0082】
比較例D:溶媒精製したパラフィン基礎油に、8mM/kgのシェブロン・ケミカル社から市販されているジチオ燐酸亜鉛、及び3mM/kgのシェブロン・ケミカル社からの過塩基性カルシウムフェネートを混合した。最終油混合物は、40℃で約46cStの動粘性率を持っていた。
【0083】
例5:比較例Dの最終油に、0.10重量%の市販N−オレイル−1,3−プロパンジアミンを添加した。
【0084】
例6:比較例Dの最終油に、0.05重量%の市販2−(ヘプタデセニル)−4,5−ジヒドロ−1H−イミダゾール−1−エタノールを添加した。
【0085】
例7:比較例Dの最終油に、0.10重量%の市販ペンタエリトリトールモノオレエートを添加した。
【0086】
例8:比較例Dの最終油に、0.10重量%の市販ソルビタンモノオレエートを添加した。
【0087】
例9:比較例Dの最終油に、0.50重量%の市販オレイルアミンを添加した。
【0088】
上記実施例を実験室ポンプ試験装置で評価した。この評価のために用いた試験ポンプは、オハイオ州メリースビルのデニソン・ハイドローリックスによって製造されたP46型軸ピストンポンプであった。短時間の試運転の後、ポンプを5000±100psiに維持した作動ループ圧力で操作した。P46入口温度を60時間160±10°Fに制御し、次に40時間210±10°Fに制御した。次にポンプ部品を表面疲労について検査した。面板又はポートプレートに対する損傷、又はピストンシューズ(piston shoes)の過度の擦り傷及び(又は)黄銅のクリーププレートへの移行は損傷として記録した。
【0089】
次の表は試験結果を要約したものである。
Figure 0004080056
境界的不合格とは、合格の条件の全てではないが幾つかは満足していることを意味する。
【0090】
本発明を特定の態様に関して記述してきたが、特許請求の範囲から離れることなく、当業者により行うことができる種々の変更及び置き換えを包含するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydraulic fluid that provides improved wear protection to a piston pump.
[0002]
[Prior art]
Hydraulic fluid devices are used in both moving and stationary devices. These devices have hydraulic cylinders, valves, pumps, piping, filters, and reservoirs. The pump pressurizes and sends hydraulic fluid to actuators, motors and / or hydraulic cylinders to provide motion and position control of the machine parts. In many devices, the hydraulic fluid also serves as a lubricant that provides protection against wear.
[0003]
Pumps in high pressure devices are generally of two types, rotary vane pumps and / or axial piston pumps. High pressure vane pumps require a hydraulic fluid that is non-wearing and oxidatively stable. These properties are generally achieved by using zinc dithiophosphate in the hydraulic fluid. Piston-type pumps require additives for rust and oxidation prevention but do not require the use of zinc dithiophosphate. Conversely, fluids containing zinc dithiophosphate have been found to be detrimental to the sliding steel-copper alloy interface in certain piston pumps. In some cases this results in premature catastrophic damage of such pumps.
[0004]
One solution for this has been to develop alternative lubricating compositions for high hydraulic piston pumps and vane pumps. These separate compositions are not satisfactory for both types of pumps. The vane pump requires a lubricant containing an antiwear agent such as zinc dithiophosphate, which corrodes the copper alloy parts of the piston pump. Rust and antioxidant oils are sufficient for use in piston pumps but do not contain additives with sufficient surface reactivity to prevent wear of the steel parts of the vane pump.
[0005]
The second solution was to develop a fluid that would give a slight performance with both types of pumps. There has been a long felt need for a more powerful single hydraulic pump lubricant, especially in applications where two types of pumps draw their lubricant from the same reservoir.
[0006]
An example of this second solution is described by Peeler in US Pat. No. 4,622,157 entitled “Hydraulic Fluid System With Piston And Vane Pumps”. Are listed. Peeler describes the use of hydraulic fluids containing oils of lubricating viscosity, zinc dithiophosphate and sulfurized ester olefins in applications where both types of pumps are intended to draw their lubricant from the same reservoir. Yes. Although this hydraulic fluid is useful for both types of pumps, the combination of zinc dithiophosphate and sulfurized ester olefins can degrade the thermal stability of the hydraulic fluid.
[0007]
In JP-A-5-331477 (1993) by Tonen Corporation, (a) 0.1 to 7% by weight of one or a mixture of zinc dithiophosphate, phosphite, and phosphate, and (b) A hydraulic oil composition specifically described for power steering fluids containing 0.02 to 3 wt% glycerin aliphatic ester is described. The purpose of the glycerin ester is to reduce friction. The publication does not teach or suggest the use of the hydraulic oil composition in a hydraulic system having both a rotary vane pump and an axial piston pump.
[0008]
U.S. Pat. No. 4,210,541 entitled “Stabilized Hydraulic Fluid Composition” includes (a) a base oil and (b) 0.1 to 2.0 vol% C. Four ~ C 12 Non-abrasive hydraulic pressure comprising bis (dialkyldithiophosphate) zinc, (c) 0.01-1.0% by volume metal dialkylnaphthalene sulfonate, and (d) 0.01-1.0% by weight fatty acid imidazoline. Oil is listed. This patent does not teach or suggest the use of the hydraulic oil composition in a hydraulic system having both a rotary vane pump and an axial piston pump.
[0009]
U.S. Pat. No. 4,210,542 entitled “Multicomponent Stabilized Hydraulic Fluid” includes (a) a base oil and (b) 0.1 to 2.0 vol% C. Four ~ C 12 A non-abrasive hydraulic oil comprising bis (dialkyldithiophosphate) zinc, (c) 0.01-1.0% by volume metal phosphonate, and (d) 0.01-1.0% by weight fatty acid imidazoline. Are listed. This patent does not teach or suggest the use of the hydraulic oil composition in a hydraulic system having both a rotary vane pump and an axial piston pump.
[0010]
US Pat. No. 4,530,771 entitled “Lubricating Oil Compositions” describes a lubricating oil composition comprising a borated glycerin ester to conserve fuel in a crankcase engine. Has been. It does not teach a hydraulic oil composition.
[0011]
[Problems to be solved by the invention]
The present invention provides a non-abrasive hydraulic fluid that can be satisfactorily used in both vane pumps and piston pumps. The non-abrasive hydraulic fluid is used in a hydraulic device having a piston-type pump having a wear surface comprising copper or a copper alloy, and optionally a vane-type pump having a wear surface comprising steel. In one embodiment, the hydraulic device has both a piston-type pump and a vane-type pump, and the hydraulic fluid is drawn from a common reservoir. The present invention also provides a method of providing lubrication to both piston and vane pumps, and is particularly attractive for use in hydraulic systems having a combination of piston and vane pumps.
[0012]
[Means for Solving the Problems]
Non-abrasive hydraulic fluid is useful for both types of pumps. It contains a major amount of an oil of lubricating viscosity, a minor amount of at least one metal dithiophosphate, and a minor amount of an anti-wear agent. Alternatively, the non-abrasive hydraulic fluid can be made by mixing a major amount of an oil of lubricating viscosity, a small amount of at least one metal dithiophosphate, and an anti-wear agent. Since the components may interact, the hydraulic fluid may contain one or more complexes or reaction products of the various components along with the unreacted components.
[0013]
Normally, the use of metal dithiophosphates in hydraulic fluids will cause adhesives and / or corrosive wear of the piston pump copper alloy parts, but the presence of special wear mitigants is usually accompanied by We have found that metal dithiophosphates can be used without causing wear problems.
[0014]
The metal dithiophosphate is preferably a zinc dialkyldithiophosphate having an alkyl group having less than 9 carbon atoms. The non-abrasive hydraulic fluid preferably comprises 2-10 mM / kg, more preferably 4-6 mM / kg metal dithiophosphate. Preferably, the zinc dialkyldithiophosphate is derived from a primary alcohol branched at the β-carbon, such as zinc di-2-ethylhexyl dithiophosphate.
[0015]
Abrasion reducers
(1) an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof;
(2) a nitrogen-containing compound selected from the group consisting of aliphatic amines, aliphatic polyamines, aliphatic imidazolines, and mixtures thereof; and
(3) A mixture of (1) and (2),
Selected from the group consisting of
[0016]
In each case of the wear reducer, the aliphatic group is substantially linear and the wear reducer has at least 10 carbon atoms. Aliphatic groups may or may not be saturated and they may or may not be substituted.
[0017]
The non-abrasive hydraulic fluid preferably contains 0.01 to 0.5% by weight, more preferably 0.025 to 0.25% by weight, and most preferably 0.05 to 0.1% by weight of an anti-wear agent. To do.
[0018]
The aliphatic group of the wear reducing agent is substantially free of sulfur, but in a less preferred embodiment, the aliphatic group may contain sulfurized unsaturation.
[0019]
The antiwear agent preferably has 10 to 40 carbon atoms. More preferably it contains 14 to 24 carbon atoms.
[0020]
In one embodiment, the wear reducing agent is an aliphatic polyol ester, a boric acid derivative of an aliphatic polyol ester, or a mixture of an aliphatic polyol ester and a boric acid derivative of an aliphatic polyol ester. Preferably the antiwear agent is a monoester of a polyol, for example glycerin monooleate or pentaerythritol monooleate. The wear reducing agent may be borated glycerin monooleate or borated pentaerythritol monooleate.
[0021]
In another aspect, the wear reducing agent is an aliphatic amine, an aliphatic polyamine, an aliphatic imidazoline, or a mixture thereof. Preferably the wear reducer is a fatty acid amine, such as oleylamine, a fatty acid diamine, such as N-oleyl-1,3-propanediamine, or 2- (aliphatic) -4,5-dihydro-1H-imidazole-1-alkanol. For example, 2- (heptadecyl) -4,5-dihydro-1H-imidazole-1-ethanol.
[0022]
In yet another embodiment, the wear reducer comprises: (1) an aliphatic polyol ester, a boric acid derivative thereof, or a mixture thereof; and (2) an aliphatic amine, an aliphatic polyamine, an aliphatic imidazoline, or a mixture thereof. It is.
[0023]
In another aspect, the hydraulic fluid is used in a hydraulic device having both a piston-type pump and a vane-type pump, where the piston-type pump has a wear surface comprising copper or a copper alloy, and the vane-type pump Has a steel-containing wear surface. In this embodiment, the hydraulic fluid is drawn from a common reservoir.
[0024]
An object of the present invention is to provide a single hydraulic pump lubricant useful in hydraulic systems having both types of pumps. It is particularly useful when the pumps are adapted to draw their lubricant from a common reservoir.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
As a broad aspect, the invention relates to a hydraulic device using a unique non-abrasive hydraulic fluid having a piston-type pump having a wear surface comprising copper or a copper alloy, and optionally a vane-type pump having a wear surface comprising steel. Is included. In one embodiment, the hydraulic device has both a piston-type pump and a vane-type pump, and hydraulic fluid is drawn from a common reservoir for both types of pumps.
[0026]
pump
Piston and vane pumps are well known in the art and are available from many different suppliers. The vane type pump requires that the hydraulic fluid contain an antiwear agent such as zinc dithiophosphate to protect the vane and cam ring, which are typically made of steel. However, some piston pumps, such as those manufactured by Denison Hydraulics, use a copper alloy on a steel sliding contact that is antagonized by a fluid containing such an anti-wear agent. Yes. Users of hydraulic systems want a single fluid that can be used with both types of pumps.
[0027]
The hydraulic fluid used in the present invention can be any of these known piston type and blade type pumps. In particular, it can be used in piston-type pumps with wear surfaces comprising copper or copper alloys and vane-type pumps with wear surfaces comprising steel. These piston-type and vane-type pumps are described by Peeler in US Pat. No. 4,622,157, which is hereby incorporated by reference in its entirety for all purposes.
[0028]
Non-abrasive hydraulic fluid
The non-abrasive hydraulic fluid used in the present invention is an aliphatic polyol ester, a boric acid derivative of an aliphatic polyol ester, an aliphatic polyol, with a main component amount of oil of lubricating viscosity, a small amount of metal dithiophosphate, and a small amount of wear reducer. A wear reducing agent that is an amine, an aliphatic polyamine, an aliphatic imidazoline, or a mixture thereof.
[0029]
Oil of lubricating viscosity
The non-abrasive hydraulic fluid used in the present invention contains a main component amount of oil having a lubricating viscosity. The oil may be any hydrocarbon-based lubricating oil or synthetic base oil stock. It may be derived from synthetic or natural raw materials and may be paraffinic, naphthenic, asphalt or mixtures thereof.
[0030]
Oils of lubricating viscosity can be produced from crude mineral oils by physical separation methods such as distillation, deasphalting and dewaxing. Alternatively, it can be produced by chemical conversion, such as catalytic or non-catalytic hydrotreating of mineral oil fractions, or by a combination of physical separation methods and chemical conversion. Or it may be a synthetic hydrocarbon base oil. The oil of lubricating viscosity preferably has a Kinematic Viscosity of 5 to 220 cSt at 40 ° C.
[0031]
Metal dithiophosphate
The non-abrasive hydraulic fluid used in the present invention contains a small amount of metal dithiophosphate. Preferably the metal dithiophosphate is a commercially available Group II metal dithiophosphate, and the Group II metal is preferably zinc, magnesium, calcium or barium. Most preferably, the metal is zinc.
[0032]
Metal dithiophosphates are well known extreme pressure (EP) additives and are organic substituted metal dithiophosphates, preferably metal dihydrocarbyl dithiophosphates, in which the hydrocarbyl group is 3-20 carbon atoms, Preferably it has 4 to 12 carbon atoms. As is well known in the art, mixtures of various metal compounds can also be used. Organic substituted metal dithiophosphates have aliphatic groups with functional groups such as carboxy, hydroxy, carbalkoxy and the like. The hydrocarbyl group may be aliphatic, alicyclic, or aromatic, or a mixture thereof.
[0033]
Most preferably, the metal dithiophosphate is a zinc dialkyldithiophosphate in which the alkyl group has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably less than 9. A preferred zinc compound is a zinc dialkyldithiophosphate derived from a primary alcohol branched at the β-carbon, such as zinc di-2-ethylhexyl dithiophosphate.
[0034]
The metal dithiophosphate compound is generally present at a concentration of 2 to 10 mM, preferably 3 to 8 mM, more preferably 4 to 6 mM per kg of oil, in which case there are two phosphorus atoms and one single atom in each metal dithiophosphate molecule. Assume that there are metal atoms. In this calculation method, the metal dithiophosphate concentration is determined by measuring the phosphorus content. This method of expressing the metal dithiophosphate concentration is based on the recognition that commercially available metal dithiophosphates are generally a mixture of neutral and basic materials, and therefore some of the commercially available materials used are per atom of metal. Less than two atoms of phosphorus may be present.
[0035]
Abrasion reducer
The non-abrasive hydraulic fluid used in the present invention also contains a small amount of an abrasion reducing agent. Abrasion reducer
(1) an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof;
(2) a nitrogen-containing compound selected from the group consisting of aliphatic amines, aliphatic polyamines, aliphatic imidazolines, and mixtures thereof; and
(3) A mixture of (1) and (2),
Selected from the group consisting of For example, the wear reducing agent can be a mixture of an aliphatic polyol ester and an aliphatic imidazoline.
[0036]
The aliphatic groups of the wear reducing agent are substantially linear and the wear reducing agent contains at least 10 carbon atoms. The aliphatic group may be saturated or unsaturated and may have a slight degree of branching. Aliphatic groups may be unsubstituted or they may be substituted with functional groups such as carboxy, hydroxy, carbalkoxy and the like. Preferably, the aliphatic group is substantially free of sulfur, but in a less preferred embodiment, the aliphatic group may contain sulfurized unsaturation.
[0037]
The non-abrasive hydraulic fluid preferably contains 0.01 to 0.5% by weight of a wear reducer. More preferably it contains 0.025 to 0.25% by weight of an antiwear agent. Most preferably it contains 0.05 to 0.1% by weight of an antiwear agent.
[0038]
In one embodiment, the wear reducing agent can be an aliphatic polyol ester, a boric acid derivative of an aliphatic polyol ester, or a mixture of an aliphatic polyol ester and / or their boric acid derivative. Preferably the wear reducing agent has 10 to 40 carbon atoms, more preferably 14 to 24 carbon atoms.
[0039]
Aliphatic polyol esters can be prepared by esterifying polyhydric alcohols with saturated or unsaturated monocarboxylic acids having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, provided that It is assumed that at least one hydroxyl group remains unesterified.
[0040]
Polyhydric alcohols include: ethylene glycol including di-, tri-, and tetra-ethylene glycol; propylene glycol including di-, tri-, and tetra-propylene glycol; glycerin; trimethylolpropane; butanediol; hexane Diols; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritol, including di- and tri-pentaerythritol. Preferably the triol is glycerin, pentaerythritol, trimethylolpropane or sorbitol.
[0041]
Examples of monocarboxylic acids include fatty carboxylic acids. Fatty acid esters can be produced by various methods well known in the art. Many of these esters are produced on a commercial scale. The esters used in the present invention are soluble in oil and, as found in natural products, C 6 ~ C 30 It is preferably produced from fatty acids or mixtures thereof. The fatty acid may or may not be saturated. Certain compounds found in acids from natural sources include licanoic acid, which contains one keto group. Preferred fatty acids are of the formula R 1 -COOH (wherein R 1 Is an alkyl or alkenyl) fatty acid. Examples of preferred fatty acids are acids from olein, stearin, palmiticin, myristic, palmitole, linolein, laurin, and eleostearin and natural products such as tallow, palm oil, olive oil, peanut oil, corn oil, cow leg oil, etc. It is. Often the acid is commercially available as a mixture of one or more acids.
[0042]
Specific examples of suitable esterified polyhydric alcohols include sorbitol oleate, including mono- and di-oleate; sorbitol stearate, including mono- and di-stearate; glycerol mono- and di-oleate Glycerin oleate; and erythritol octoate. Preferred examples are glycerin monooleate and pentaerythritol monooleate, and their borated derivatives.
[0043]
The aliphatic polyol ester is preferably a monoester, but di- and tri-esters can be part of the mixture. The mixture of mono- and di-esters preferably contains at least 40% by weight of monoester. Most preferably, the mixture of mono- and di-esters contains 40-60% by weight monoester. For example, commercial glycerin monooleate contains a mixture of 45-55% by weight monoester and 55-45% by weight diester.
[0044]
Suitable borate esters are described in US Pat. No. 4,530,771, cited above, which is hereby incorporated by reference in its entirety for all purposes.
[0045]
The boric acid ester useful in the present invention may include various compounds whose structure varies depending on the type of reactant, introduction ratio, and reaction conditions. They may be used alone or in combination.
[0046]
When the polyol is glycerin, typical borate esters are compounds represented by the following formulas (I) and (II) or mixtures thereof.
[0047]
[Chemical 1]
Figure 0004080056
[0048]
[Chemical 2]
Figure 0004080056
[0049]
In which X, Y and Z are independently OH groups or
[0050]
[Chemical 3]
Figure 0004080056
[0051]
R ′ represents a saturated or unsaturated aliphatic group having 7 to 23 carbon atoms.
[0052]
The boric acid ester used in the present invention is, for example, the following method:
(A) reacting a polyol ester and boric acid at a temperature of 100 ° C. to 230 ° C .;
(B) reacting a polyol with boric acid, and further reacting the resulting compound with a carboxylic acid, a lower alcohol ester of a carboxylic acid, or a carboxylic acid halide,
(C) reacting a mixture of a polyol, a carboxylic acid triester of polyol, and boric acid at a temperature of about 240 ° C to 280 ° C;
It can be manufactured by a method.
[0053]
In another embodiment, the wear reducing agent may be a nitrogen compound, such as an aliphatic amine, an aliphatic polyamine, an aliphatic imidazoline, or a mixture thereof. The wear reducer preferably has 10 to 40 carbon atoms, more preferably 14 to 24 carbon atoms.
[0054]
Aliphatic amines have the general formula R ″ NH 2 Wherein the R ″ group can be derived from a fatty acid. Preferred R ″ groups are lauric acid, myristic acid, palmitic acid, stearic acid, palmitolic acid, oleic acid, linoleic acid, linolenic acid. It is derived from more common naturally occurring fatty acids including acids, eleostearic acid and the like. More preferably, the aliphatic amine is oleylamine.
[0055]
The aliphatic polyamine used in the present invention preferably has at least one terminal amino nitrogen atom. Aliphatic polyamines have 10 to 40, preferably 14 to 24, total carbon atoms and at least two nitrogen atoms in the molecule. In each case, the amino nitrogens are separated from each other by at least two carbon atoms. The polyamine portion of the aliphatic polyamine preferably has a carbon to nitrogen ratio of about 1: 1 to 2: 1. At least one of the basic nitrogen atoms of the polyamine moiety should be a primary or secondary amino nitrogen. Suitable polyamine moieties for the aliphatic polyamines of the present invention are US Pat. Nos. 4,191,537 by Lewis and Honnen and US Pat. No. 5,413,614 by Cherpeck. (These are incorporated herein by reference for all purposes). Preferably, the aliphatic polyamine is an aliphatic ethylenediamine, an aliphatic propanediamine, or an aliphatic diethylenetriamine. A particularly preferred specific example is N-olein-1,3-propanediamine.
[0056]
A preferred class of nitrogen compounds are aliphatic imidazolines, as described in US Pat. Nos. 4,210,541 and 4,210,542, cited above. Both of these patents are hereby incorporated by reference in their entirety for all purposes.
[0057]
Aliphatic imidazolines have the general formula:
[0058]
[Formula 4]
Figure 0004080056
[0059]
(In the formula, n is an integer of 0 to 3, preferably 1, and R is an aliphatic group having 7 to 35 carbon atoms, preferably 9 to 23 carbon atoms.)
It is preferably 2- (aliphatic) -4,5-dihydro-1H-imidazole-1-alkanol having Preferred R groups are lauric acid, myristic acid, palmitic acid, stearic acid, palmitolic acid, oleic acid, linoleic acid, linolenic acid, since the R group can be derived from fatty acids in a way to produce the compound. It is derived from more common natural fatty acids including eleostearic acid. Preferably the aliphatic imidazoline is 2- (heptadecyl) -4,5-dihydro-1H-imidazole-1-ethanol.
[0060]
However, in general, aliphatic imidazolines will be a mixture of compounds. This is because most naturally occurring fatty acids are generally obtained as a mixture. For example, a mixture of stearic acid, palmitic acid, and oleic acid is obtained from tallow. Thus, aliphatic imidazolines made from tallow fatty acids are a mixture of compounds where R is hexadecyl, octadecyl, and 9-octadecyl.
[0061]
The polar group of the wear reducing agent is preferably at the end of the aliphatic group, even if it is an ester group or a nitrogen-containing group.
[0062]
Other additives
Other additives well known in the art may be present in the non-abrasive hydraulic fluid used in the present invention. For example, these additives include antioxidants, viscosity index improvers, dispersants, detergents, rust inhibitors, demulsifiers, foam inhibitors, corrosion inhibitors, pour point depressants, and other antiwear agents. Is included. Examples of these additives are shown below.
[0063]
Antioxidants: sterically hindered alkylphenols such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, and 2,6-di-t-butyl-4- ( 2-octyl-3-propanoic) phenol; N, N-di (alkylphenyl) amine; and alkylated phenylenediamine.
[0064]
Viscosity index improvers; polymeric alkyl methacrylates and olefin copolymers such as ethylene propylene copolymers or styrene butadiene copolymers are included.
[0065]
Dispersants: include hydrocarbyl succinimides, succinates, or benzylamines, where the hydrocarbyl group is an alkyl or alkenyl group having a molecular weight of about 700-3000. These compounds may be further reacted with boric acid.
[0066]
Detergent: Includes calcium alkylsalicylate and calcium alkylphenates.
[0067]
Rust inhibitors: alkenyl succinic acids, their partial esters, and their nitrogen derivatives; and synthetic alkyl aryl sulfonates such as metal dinonyl naphthalene sulfonates.
[0068]
Demulsifiers: include alkoxylated phenols and phenol formaldehyde resins and synthetic alkyl aryl sulfonates such as metal dinonyl naphthalene sulfonates.
[0069]
Antifoaming agents: include alkyl methacrylate polymers and dimethyl silicone polymers.
[0070]
Corrosion inhibitors: 2,5-dimercapto-1,3,4-thiadiazole and derivatives, mercaptobenzothiazole, alkyltriazole, and benzotriazole are included.
[0071]
Pour point depressant: Includes polymethacrylate.
[0072]
Other antiwear agents: include aryl phosphates and phosphites, sulfurized esters, and sulfur / phosphorous compounds.
[0073]
In one embodiment, the non-abrasive hydraulic fluid used in the present invention can be produced by mixing an oil of lubricating viscosity, a metal dithiophosphate, an anti-wear agent, and other additives. In another aspect, the non-abrasive hydraulic fluid is a rich, mixed metal dithiophosphate, anti-wear agent, and other additives and a small amount of diluent oil, such as kerosene, diesel fuel, or aromatic solvent. A thick additive solution may be mixed with an oil of lubricating viscosity. Since the components can interact, the hydraulic fluid may include one or more complexes or reaction products of the various components along with the unreacted components.
[0074]
【Example】
The invention is further illustrated by the following examples describing particularly advantageous process embodiments. While the examples are provided to illustrate the present invention, they are not intended to limit the invention.
[0075]
Comparative Example A: Base additive formulation comprising a mixture of zinc di-2-ethylhexyl dithiophosphate and a functionally effective amount of calcium detergent, rust inhibitor, demulsifier, antioxidant, and antifoam additive. Was mixed into the paraffin base oil so that the base additive formulation comprised 0.80% by weight of the final oil mixture. The final oil mixture had a kinematic viscosity of about 46 cSt at 40 ° C.
[0076]
Example 1: To the final oil of Comparative Example A, 0.05 wt% commercial glycerin monooleate was added.
[0077]
Comparative Example B: 4 mM / kg commercial zinc dithiophosphate and 2 mM / kg overbased calcium phenate were mixed in solvent-refined paraffin base oil. The final oil mixture had a kinematic viscosity of about 46 cSt at 40 ° C.
[0078]
Example 2: The final oil of Comparative Example B was mixed with 0.10 wt% commercial glycerin monooleate.
[0079]
Comparative Example C: Commercial non-abrasive hydraulic pressure comprising a mixture of zinc di-2-ethylhexyl dithiophosphate and a functionally effective amount of calcium detergent, rust inhibitor, demulsifier, antioxidant, and antifoam additive. The oil base additive formulation was mixed into the solvent-refined paraffin base oil such that the base additive formulation comprised 1.13% by weight of the final oil mixture. The final oil mixture had a kinematic viscosity of about 46 cSt at 40 ° C.
[0080]
Example 3 To the final oil of Comparative Example C was added 0.10 wt% borated glycerin monooleate.
[0081]
Example 4: To the final oil of Comparative Example C, 0.10 wt% of commercially available N-oleyl-1,3-propanediamine was added.
[0082]
Comparative Example D: Solvent-purified paraffin base oil was mixed with 8 mM / kg zinc dithiophosphate commercially available from Chevron Chemical Company and 3 mM / kg overbased calcium phenate from Chevron Chemical Company. The final oil mixture had a kinematic viscosity of about 46 cSt at 40 ° C.
[0083]
Example 5: To the final oil of Comparative Example D, 0.10% by weight of commercially available N-oleyl-1,3-propanediamine was added.
[0084]
Example 6 To the final oil of Comparative Example D, 0.05% by weight of commercially available 2- (heptadecenyl) -4,5-dihydro-1H-imidazole-1-ethanol was added.
[0085]
Example 7: To the final oil of Comparative Example D, 0.10 wt% of commercial pentaerythritol monooleate was added.
[0086]
Example 8: To the final oil of Comparative Example D, 0.10% by weight of commercial sorbitan monooleate was added.
[0087]
Example 9: To the final oil of Comparative Example D, 0.50 wt% commercial oleylamine was added.
[0088]
The above examples were evaluated with a laboratory pump test apparatus. The test pump used for this evaluation was a P46 axial piston pump manufactured by Denison Hydrox of Marysville, Ohio. After a short test run, the pump was operated at a working loop pressure maintained at 5000 ± 100 psi. The P46 inlet temperature was controlled to 160 ± 10 ° F. for 60 hours and then to 210 ± 10 ° F. for 40 hours. The pump parts were then inspected for surface fatigue. Damage to the face plate or port plate, or excessive abrasion of piston shoes and / or the transition of brass to the creep plate was recorded as damage.
[0089]
The following table summarizes the test results.
Figure 0004080056
Boundary failure means that some but not all of the conditions for passing are satisfied.
[0090]
While this invention has been described in terms of particular embodiments, it is intended to encompass various modifications and substitutions that can be made by those skilled in the art without departing from the scope of the claims.

Claims (24)

銅又は銅合金を含む摩耗性表面を有するピストン型ポンプ及び鋼を含む摩耗性表面を有する羽根型ポンプを有する油圧装置において、両方の型のポンプで有用な非摩耗性油圧流体で、
(a) 主成分量の潤滑粘度の油、
(b) 少量の少なくとも一種類の金属ジチオ燐酸塩、及び
(c) 少量の摩耗軽減剤で、
(1) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(2) 脂肪族アミン、脂肪族ポリアミン及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(3) (1)及び(2)の混合物、
からなる群から選択され、然も、前記脂肪族基が実質的に直鎖である摩耗軽減剤で、少なくとも10個の炭素原子を有する摩耗軽減剤、
を含む非摩耗性油圧流体を前記油圧装置中で用いることからなる改良油圧装置。
A hydraulic device comprising a vane type pump having a wear surface comprising a piston-type pump and steel having a wear surface comprising copper or a copper alloy, in both types of pumps useful nonabrasive hydraulic fluid,
(A) the main component amount of oil of lubricating viscosity;
(B) a small amount of at least one metal dithiophosphate, and (c) a small amount of wear reducer,
(1) an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof;
(2) aliphatic amines, aliphatic polyamine down及 beauty nitrogen-containing compound selected from the group consisting of mixtures, and mixtures of (3) (1) and (2),
An anti-wear agent having at least 10 carbon atoms, wherein the anti-aliphatic group is substantially linear and is selected from the group consisting of:
An improved hydraulic system comprising using a non-abrasive hydraulic fluid containing in the hydraulic system.
金属ジチオ燐酸塩がジアルキルジチオ燐酸亜鉛であり、ジアルキルジチオ燐酸亜鉛のアルキル基が、9個より少ない炭素原子を有し、非摩耗性油圧流体が前記ジチオ燐酸亜鉛を2〜10mM/kg含有する、請求項1に記載の油圧装置。  The metal dithiophosphate is zinc dialkyldithiophosphate, the alkyl group of the zinc dialkyldithiophosphate has less than 9 carbon atoms, and the non-abrasive hydraulic fluid contains 2-10 mM / kg of said zinc dithiophosphate, The hydraulic device according to claim 1. ジアルキルジチオ燐酸亜鉛が、β−炭素の所で分岐している第一級アルコールから誘導されたものであり、非摩耗性油圧流体が前記ジチオ燐酸亜鉛を4〜6mM/kg含有する、請求項2に記載の油圧装置。  The zinc dialkyldithiophosphate is derived from a primary alcohol branched at the β-carbon and the non-abrasive hydraulic fluid contains 4-6 mM / kg of the zinc dithiophosphate. Hydraulic device as described in. ジアルキルジチオ燐酸亜鉛がジ−2−エチルヘキシルジチオ燐酸亜鉛である、請求項3に記載の油圧装置。  The hydraulic device according to claim 3, wherein the zinc dialkyldithiophosphate is zinc di-2-ethylhexyldithiophosphate. 非摩耗性油圧流体が、0.05〜0.1重量%の摩耗軽減剤を含有する、請求項1に記載の油圧装置。  The hydraulic device of claim 1, wherein the non-abrasive hydraulic fluid contains 0.05 to 0.1 wt% wear reducer. 摩耗軽減剤の脂肪族基が実質的に硫黄を含まない、請求項1に記載の油圧装置。  The hydraulic device according to claim 1, wherein the aliphatic group of the wear reducing agent is substantially free of sulfur. 摩耗軽減剤が10〜40個の炭素原子を有する、請求項1に記載の油圧装置。  The hydraulic device according to claim 1, wherein the wear reducing agent has 10 to 40 carbon atoms. 摩耗軽減剤が、脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物からなる群から選択されたものである、請求項1に記載の油圧装置。  The hydraulic device according to claim 1, wherein the wear reducing agent is selected from the group consisting of an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof. 摩耗軽減剤が、ポリオールのモノエステル又はその硼酸化誘導体である、請求項8に記載の油圧装置。  The hydraulic device according to claim 8, wherein the wear reducing agent is a monoester of polyol or a borated derivative thereof. 摩耗軽減剤が、グリセリンモノオレエート、硼酸化グリセリンモノオレエート、ペンタエリスリトールモノオレエート、及び硼酸化ペンタエリスリトールモノオレエートからなる群から選択されたものである、請求項9に記載の油圧装置。  The hydraulic device according to claim 9, wherein the wear reducing agent is selected from the group consisting of glycerin monooleate, borated glycerin monooleate, pentaerythritol monooleate, and borated pentaerythritol monooleate. . 摩耗軽減剤が、脂肪族アミン、脂肪族ポリアミン及びそれらの混合物からなる群から選択されたものである、請求項1に記載の油圧装置。Wear-reducing agent is one selected from the group consisting of aliphatic amines, aliphatic polyamine down及 beauty mixtures thereof The device of claim 1. 摩耗軽減剤がオレイルアミンである、請求項11に記載の油圧装置。  The hydraulic device of claim 11, wherein the wear reducing agent is oleylamine. 摩耗軽減剤がN−オレイル−1,3−プロパンジアミンである、請求項11に記載の油圧装置。  The hydraulic device according to claim 11, wherein the wear reducing agent is N-oleyl-1,3-propanediamine. 方の型のポンプで用いるための共通の溜めが存在し、前記共通の溜め中に非摩耗性油圧流体を用いる、請求項1に記載の油圧装置。Common reservoir is present for use in both types of pumps, using a non-abrasive hydraulic fluid in said common reservoir, hydraulic system according to claim 1. 銅又は銅合金を含む摩耗性表面を有するピストン型ポンプ及び鋼を含む摩耗性表面を有する羽根型ポンプを有する油圧装置において、前記油圧装置中で、前記両方の型のポンプに有用な非摩耗性油圧流体を用いることからなり、然も前記非摩耗性油圧流体が、次の成分、
(a) 主成分量の潤滑粘度の油、
(b) 少量の少なくとも一種類の金属ジチオ燐酸塩、及び
(c) 少量の摩耗軽減剤で、
(1) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(2) 脂肪族アミン、脂肪族ポリアミン、及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(3) (1)及び(2)の混合物、
からなる群から選択され、然も、前記脂肪族基が実質的に直鎖である摩耗軽減剤で、少なくとも10個の炭素原子を有する摩耗軽減剤、
を混合することからなる方法により製造されたものである改良油圧装置。
A hydraulic device comprising a vane type pump having a wear surface comprising a piston-type pump and steel having a wear surface comprising copper or a copper alloy, in the hydraulic device, useful non-abrasive to the both types of pumps Using non-abrasive hydraulic fluid, the non-abrasive hydraulic fluid having the following components:
(A) the main component amount of oil of lubricating viscosity;
(B) a small amount of at least one metal dithiophosphate, and (c) a small amount of wear reducer,
(1) an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof;
(2) aliphatic amines, aliphatic polyamines,及 Beauty nitrogen-containing compound selected from the group consisting of mixtures, and mixtures of (3) (1) and (2),
An anti-wear agent having at least 10 carbon atoms, wherein the anti-aliphatic group is substantially linear and is selected from the group consisting of:
An improved hydraulic device that is manufactured by a method comprising mixing.
銅又は銅合金を含む摩耗性表面を有するピストン型ポンプ及び鋼を含む摩耗性表面を有する羽根型ポンプを有する油圧装置において、前記油圧装置中で、前記両方の型のポンプに有用な非摩耗性油圧流体を用いることからなり、然も前記非摩耗性油圧流体が、
(a) 次の成分、
(1) 少量の希釈剤油、
(2) 少なくとも一種類の金属ジチオ燐酸塩、及び
(3) 摩耗軽減剤で、
(i) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(ii) 脂肪族アミン、脂肪族ポリアミン、及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(iii) (i)及び(ii)の混合物、
からなる群から選択され、然も、前記脂肪族基が実質的に直鎖である摩耗軽減剤で、少なくとも10個の炭素原子を有する摩耗軽減剤、
を混合して濃厚物を形成し、
(b) 工程(a)で形成した濃厚物を、主成分量の潤滑粘度の油と混合する、
ことからなる方法により製造されたものである改良油圧装置。
A hydraulic device comprising a vane type pump having a wear surface comprising a piston-type pump and steel having a wear surface comprising copper or a copper alloy, in the hydraulic device, useful non-abrasive to the both types of pumps Using a hydraulic fluid, but the non-abrasive hydraulic fluid,
(A) the following ingredients:
(1) A small amount of diluent oil,
(2) at least one metal dithiophosphate, and (3) a wear reducer,
(I) aliphatic polyol esters, their boric acid derivatives, and mixtures thereof;
(Ii) aliphatic amines, mixtures of aliphatic polyamines,及 Beauty nitrogen-containing compound selected from the group consisting of a mixture, and (iii) (i) and (ii),
An anti-wear agent having at least 10 carbon atoms, wherein the anti-aliphatic group is substantially linear and is selected from the group consisting of:
To form a concentrate,
(B) mixing the concentrate formed in step (a) with a major amount of oil of lubricating viscosity;
An improved hydraulic device manufactured by a method comprising:
銅又は銅合金を含む摩耗性表面を有するピストン型ポンプ及び鋼を含む摩耗性表面を有する羽根型ポンプを有する油圧装置に潤滑を与える方法において、前記油圧装置中で、両方の型のポンプに有用な非摩耗性油圧流体を用いることからなり、然も前記非摩耗性油圧流体が、
(a) 主成分量の潤滑粘度の油、
(b) 少量の少なくとも一種類の金属ジチオ燐酸塩、及び
(c) 少量の摩耗性軽減剤で、
(1) 脂肪族ポリオールエステル、その硼酸誘導体、及びそれらの混合物、
(2) 脂肪族アミン、脂肪族ポリアミン、及びそれらの混合物からなる群から選択された窒素含有化合物、及び
(3) (1)及び(2)の混合物、
からなる群から選択され、然も、前記脂肪族基が実質的に直鎖である摩耗軽減剤で、少なくとも10個の炭素原子を有する摩耗軽減剤、
を含む、油圧装置に潤滑を与える方法。
A method of providing lubrication to the hydraulic system having a vane-type pump having an abrasive surface comprising a piston-type pump and steel having a wear surface comprising copper or a copper alloy, in the hydraulic device, useful for both types of pumps Non-abrasive hydraulic fluid, which is still non-abrasive hydraulic fluid,
(A) the main component amount of oil of lubricating viscosity;
(B) a small amount of at least one metal dithiophosphate, and (c) a small amount of wear reducer,
(1) an aliphatic polyol ester, a boric acid derivative thereof, and a mixture thereof;
(2) aliphatic amines, aliphatic polyamines,及 Beauty nitrogen-containing compound selected from the group consisting of mixtures, and mixtures of (3) (1) and (2),
An anti-wear agent having at least 10 carbon atoms, wherein the anti-aliphatic group is substantially linear and is selected from the group consisting of:
A method of providing lubrication to a hydraulic system.
非摩耗性油圧流体が4〜6mM/kgのジチオ燐酸亜鉛を含有し、前記金属ジチオ燐酸塩がジ−2−エチルヘキシルジチオ燐酸亜鉛である、請求項17に記載の方法。18. The method of claim 17 , wherein the non-abrasive hydraulic fluid contains 4-6 mM / kg zinc dithiophosphate and the metal dithiophosphate is zinc di-2-ethylhexyl dithiophosphate. 非摩耗性油圧流体が、0.05〜0.1重量%の摩耗軽減剤を含有し、前記摩耗軽減剤の脂肪族基が実質的に硫黄を含まない、請求項17に記載の方法The method of claim 17 , wherein the non-abrasive hydraulic fluid contains 0.05 to 0.1 wt% wear reducer, and the aliphatic groups of the wear reducer are substantially free of sulfur. 摩耗軽減剤を、グリセリンモノオレエート、硼酸化グリセリンモノオレエート、ペンタエリスリトールモノオレエート、及び硼酸化ペンタエリスリトールモノオレエートからなる群から選択する、請求項17に記載の方法。18. The method of claim 17 , wherein the antiwear agent is selected from the group consisting of glycerin monooleate, borated glycerine monooleate, pentaerythritol monooleate, and borated pentaerythritol monooleate. 摩耗軽減剤を、脂肪族アミン、脂肪族ポリアミン、及びそれらの混合物からなる群から選択する、請求項19に記載の方法。Wear-reducing agent is selected aliphatic amines, aliphatic polyamines, from the group consisting beauty mixtures thereof The method of claim 19. 摩耗軽減剤脂肪族ポリアミンである、請求項17に記載の方法。Wear-reducing agent is an aliphatic polyamine A method according to Motomeko 17. 摩耗軽減剤を、オレイルアミン及びN−オレイル−1,3−プロパンジアミンからなる群から選択する、請求項22に記載の方法。Wear-reducing agent is selected from oleylamine and N- oleyl-1,3 Puropanjiami down or Ranaru group, The method of claim 22. 方の型のポンプで用いるための共通の溜めが存在し、前記共通の溜め中に非摩耗性油圧流体を用いる、請求項17に記載の方法。Common reservoir is present for use in both types of pumps, using a non-abrasive hydraulic fluid in said common reservoir The method of claim 17.
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JPH10298574A (en) 1998-11-10
EP1142982A3 (en) 2001-12-12
US5849675A (en) 1998-12-15
EP0870820A1 (en) 1998-10-14
CA2231907C (en) 2007-07-31
CA2231907A1 (en) 1998-10-10
EP1142982A2 (en) 2001-10-10
SG68030A1 (en) 1999-10-19

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